Showing papers by "Stanislav V. Sinogeikin published in 2017"

Mechanochemical Synthesis of Carbon Nanothread Single Crystals

Abstract: Synthesis of well-ordered reduced dimensional carbon solids with extended bonding remains a challenge. For example, few single-crystal organic monomers react under topochemical control to produce single-crystal extended solids. We report a mechanochemical synthesis in which slow compression at room temperature under uniaxial stress can convert polycrystalline or single-crystal benzene monomer into single-crystalline packings of carbon nanothreads, a one-dimensional sp3 carbon nanomaterial. The long-range order over hundreds of microns of these crystals allows them to readily exfoliate into fibers. The mechanochemical reaction produces macroscopic single crystals despite large dimensional changes caused by the formation of multiple strong, covalent C–C bonds to each monomer and a lack of reactant single-crystal order. Therefore, it appears not to follow a topochemical pathway, but rather one guided by uniaxial stress, to which the nanothreads consistently align. Slow-compression room-temperature synthesis ...

Quantum and isotope effects in lithium metal

Abstract: The crystal structure of elements at zero pressure and temperature is the most fundamental information in condensed matter physics. For decades it has been believed that lithium, the simplest metallic element, has a complicated ground-state crystal structure. Using synchrotron x-ray diffraction in diamond anvil cells and multiscale simulations with density functional theory and molecular dynamics, we show that the previously accepted martensitic ground state is metastable. The actual ground state is face-centered cubic (fcc). We find that isotopes of lithium, under similar thermal paths, exhibit a considerable difference in martensitic transition temperature. Lithium exhibits nuclear quantum mechanical effects, serving as a metallic intermediate between helium, with its quantum effect–dominated structures, and the higher-mass elements. By disentangling the quantum kinetic complexities, we prove that fcc lithium is the ground state, and we synthesize it by decompression.

A metastable liquid melted from a crystalline solid under decompression

Abstract: A metastable liquid may exist under supercooling, sustaining the liquid below the melting point such as supercooled water and silicon. It may also exist as a transient state in solid–solid transitions, as demonstrated in recent studies of colloidal particles and glass-forming metallic systems. One important question is whether a crystalline solid may directly melt into a sustainable metastable liquid. By thermal heating, a crystalline solid will always melt into a liquid above the melting point. Here we report that a high-pressure crystalline phase of bismuth can melt into a metastable liquid below the melting line through a decompression process. The decompression-induced metastable liquid can be maintained for hours in static conditions, and transform to crystalline phases when external perturbations, such as heating and cooling, are applied. It occurs in the pressure–temperature region similar to where the supercooled liquid Bi is observed. Akin to supercooled liquid, the pressure-induced metastable liquid may be more ubiquitous than we thought. It is experimentally challenging to observe an intermediate liquid in solid–solid phase transitions due to short lifetimes of the resulting metastable states. Here, Linet al. show that a metastable bismuth liquid can be formed from a crystalline solid through decompression and maintained for hours.

Kinetically Controlled Two-Step Amorphization and Amorphous-Amorphous Transition in Ice

Abstract: We report the results of in situ structural characterization of the amorphization of crystalline ice Ih under compression and the relaxation of high-density amorphous (HDA) ice under decompression at temperatures between 96 and 160 K by synchrotron x-ray diffraction. The results show that ice Ih transforms to an intermediate crystalline phase at 100 K prior to complete amorphization, which is supported by molecular dynamics calculations. The phase transition pathways show clear temperature dependence: direct amorphization without an intermediate phase is observed at 133 K, while at 145 K a direct Ih-to-IX transformation is observed; decompression of HDA shows a transition to low-density amorphous ice at 96 K and $\ensuremath{\sim}1\text{ }\text{ }\mathrm{Pa}$, to ice Ic at 135 K and to ice IX at 145 K. These observations show that the amorphization of compressed ice Ih and the recrystallization of decompressed HDA are strongly dependent on temperature and controlled by kinetic barriers. Pressure-induced amorphous ice is an intermediate state in the phase transition from the connected H-bond water network in low pressure ices to the independent and interpenetrating H-bond network of high-pressure ices.

Direct Observations of a Dynamically Driven Phase Transition with in situ X-Ray Diffraction in a Simple Ionic Crystal.

Abstract: We report real-time observations of a phase transition in the ionic solid ${\mathrm{CaF}}_{2}$, a model $A{B}_{2}$ structure in high-pressure physics. Synchrotron x-ray diffraction coupled with dynamic loading to 27.7 GPa, and separately with static compression, follows, in situ, the fluorite to cotunnite structural phase transition, both on nanosecond and on minute time scales. Using Rietveld refinement techniques, we examine the kinetics and hysteresis of the transition. Our results give insight into the kinetic time scale of the fluorite-cotunnite phase transition under shock compression, which is relevant to a number of isomorphic compounds.

Deuterium Isotope Effects in Polymerization of Benzene under Pressure

Abstract: The enormous versatility in the properties of carbon materials depends on the content of the sp2 and sp3 covalent bonds. Under compression, if intermolecular distances cross a critical threshold, then unsaturated hydrocarbons gradually transform to saturated carbon polymers. However, the mechanism of polymerization, even for benzene, the simplest aromatic hydrocarbon, is still not understood. We used high-pressure synchrotron X-ray, neutron diffraction, and micro-Raman spectroscopy together with density functional calculations to investigate the isotope effects in benzene isotopologues C6H6 and C6D6 up to 46.0 GPa. Raman spectra of polymeric products recovered from comparable pressures show the progression of polymerization exhibiting a pronounced kinetic isotope effect. Kinetically retarded reactions in C6D6 shed light on the mechanism of polymerization of benzene. We find that C6D6-derived products recovered from P < 35 GPa actively react with moisture, forming polymers with higher sp3 hydrogen contents...

Anomalous Surface Doping Effect in Semiconductor Nanowires

Abstract: Surface doping is being used as an effective approach to improve the mechanical, optical, electronic, and magnetic properties of various materials. For example, experimental studies have proven that rare-earth element doping can enhance the optical properties of silicon nanostructures. However, the majority of previous investigations focused on either bulk materials or nanosized spherical crystals. Here we present a comparative study on semiconducting germanium (Ge) nanowires with and without surface doping by using multiple integrated characterization probes, including high resolution scanning/transmission electron microscopy (SEM/TEM), in situ high pressure synchrotron X-ray diffraction (XRD), and Raman spectroscopy. Our results reveal that under pressure the stability of the Ge-I phase (diamond structure) in erbium (Er)-doped Ge nanowires is enhanced compared to undoped Ge nanowires. We also found an increased stability of the Ge-II phase (body centered tetragonal structure) in Er-doped Ge nanowires du...

Effect of stress on melting of rhombohedral bismuth

Abstract: Pressure-induced melting of rhombohedral bismuth (Bi-I) has been investigated in the solid pressure medium of NaCl and the hydrostatic medium of neon at high temperatures by in-situ synchrotron x-ray diffraction. Upon compression from ∼0.7 GPa to 3.2 GPa at (or below) 489 K, Bi-I melts into a liquid between ∼1.2 and 1.6 GPa in the solid pressure medium and then crystallizes into Bi-IV at ∼2.9 GPa. However, at the same temperature of 489 K, Bi-I transforms to a crystalline phase (Bi-II′ or Bi-II) at ∼1.8 GPa under hydrostatic conditions, followed by a transformation to Bi-IV at 2.5 GPa. Our x-ray diffraction results indicate that the melting of Bi-I at (or below) 489 K is due to the stress. There is a stress effect on the structural deformation of Bi-I when the solid pressure medium is used, viz., pressure-dependent c/a for Bi-I in the solid pressure medium is larger or smaller than that under hydrostatic conditions. According to the classical nucleation theory, the stress provides an additional driving fo...